Transparent substrate provided with a heat-reflective multilayer stack

ABSTRACT

The subject of the invention is a flexible or rigid, transparent substrate provided with a stack of thin layers, which includes at least one functional layer predominantly based on silver Ag placed between two coatings of dielectric material, at least one of the coatings comprising a layer predominantly based on aluminium nitride AlN. The functional layer or at least one of the functional layers is modified by incorporating at least one minor metal M other than Ag and/or the said AlN-based layer, or at least one of them, is modified by incorporating at least one metal M′ in a minor amount compared with the aluminium.

[0001] The invention relates to a stack of interferential thin layers at least partly reflecting in the infrared, especially that emitted by solar radiation, and which comprises at least one “functional” layer and coatings of dielectric material which are placed on each side of the latter.

[0002] The expression “functional layer(s)” is understood within the invention to mean the layer or layers which, within the stack, have the desired thermal reflection properties and which are metallic, more particularly based on a noble metal of the Ag type.

[0003] The expression “coatings of dielectric material” is understood within the invention to mean a layer or a superposition of layers of dielectric material of the metal oxide, metal nitride or silicon nitride type, especially having the function of adjusting the optical appearance of the stack, especially of lowering the light reflection, and optionally the function of protecting the “functional” layer or layers.

[0004] Thus, the present invention relates to stacks of the type:

[0005] (dielectric coating/functional layer/dielectric coating)

[0006] this sequence being possibly repeated n times, with n=2 or 3.

[0007] The invention concerns multilayer stacks or a rigid substrate of the glass or rigid polymer, such as polycarbonates PC or polymethyl methacrylate PMMA, type. It is possible to use substrates in glazing units, by themselves or mounted as insulating or laminated glazing. However, the invention relates more a particularly to flexible substrates based on a polymer, especially polyurethane PU or polyethylene terephthalate.

[0008] Studies have already been carried out on stacks comprising silver layers interspersed with AlN and/or metal-oxide dielectrics, these multilayer stacks being deposited on PET substrates. Reference may especially be wade to Patent Application PCT/FR99/00466 filed on Mar. 2, 1999 in the name of Saint-Gobain Vitrage.

[0009] It is advantageous for all or some of the dielectric coatings used to be based on a nitride, especially the two most common in this application, namely aluminium nitride AlN or silicon nitride Si₃N₄. This is because nitride-based dielectrics are particularly stable chemically and can thus effectively fulfil the role of “barrier layer” with respect to the silver layer or layers. It is therefore advantageous to place them at least as a “sublayer” directly on the substrate and/or as an “overlayer” as the final layer of the stack.

[0010] However, their use is not without drawbacks: this is because it has been found that their adhesion to silver is not optimal, which results, moreover, in the stack being quite fragile, with the risk of delamination and problems of optical quality. One possibility of increasing this mutual adhesion consists in interposing, between the silver layer and the nitride layer, a thin layer which will act as an adhesion layer, this thin layer being, for example, made of a metal of the Ti type, which does not necessarily have to be continuous. This possibility gives good results, but increases the number of layers in the stack.

[0011] The object of the invention is therefore to remedy the abovementioned drawbacks, especially to improve the quality of the stacks of thin layers comprising both silver-based layers and nitride-based layers, without causing difficulties or complications in their manufacture on an industrial scale.

[0012] The subject of the invention is firstly a flexible or rigid, transparent substrate provided with a stack of thin layers, which includes at least one functional layer predominantly based on silver Ag placed between two coatings of dielectric material, at least one of the coatings comprising a layer predominantly based on aluminium nitride AlN. According to the invention, the functional layer (or at least one of the functional layers) is chemically modified by incorporating at least one minor metal M other than Ag.

[0013] Alternatively or in addition, the AlN-based layer (or at least one of the AlN-based layers) is also chemically modified by incorporating at least one minor metal M′ other than aluminium Al.

[0014] The metal M and the metal M′ may be incorporated by using (as moreover for all the other layers in the stack) the known vacuum deposition technique of sputtering, preferably magnetic-field-enhanced sputtering: what is then provided is, respectively, a silver target alloyed with the metal M in question (deposition in an inert atmosphere, possibly containing nitrogen) and an aluminium target alloyed with the metal M′ in question (deposition of the nitride in a nitriding reactive atmosphere, containing nitrogen).

[0015] The term “metal” within the meaning of the invention includes silicon. To make the targets, the alloy may be made in a known manner by sintering a mixture of powders of the metals in question. The Al target may also be partially covered with the metal in question.

[0016] It has thus proved possible to increase the affinity between the silver and the metal nitrides, such as AlN, by slightly modifying one or both, this modification being sufficient for them to adhere significantly better to each other, but being sufficiently moderate not to cause any deterioration in the desired properties of these materials (optical and thermal properties). It is thus conceivable to dispense with additional layers being interposed between them to facilitate their mutual adhesion, this being a great advantage from the industrial standpoint since the fewer the number of layers, the greater the production efficiency and the more compact the production line may be.

[0017] The invention applies most particularly to stacks containing n functional layers and (n+1) dielectric coatings with: n≧1, especially n=1, n=2 or n>2. As recalled in the preamble of this text, the substrates may be rigid or flexible.

[0018] The metal M that can be incorporated into the silver-based layer is aluminium, copper or gold. Preferably, between 0.1 and 10%, especially between 0.5 and 2%, by weight of the metal M is added to the silver layer.

[0019] The metal M′ that can be incorporated into the AlN-based layer is chosen from at least one of the following metals: Zn, Ti, Sn, Mn, Mg, Ag. It is preferred to add approximately 0.1 to 10%, especially 0.5 to 2%, by weight of the metal M′ with respect to the aluminium of the layer.

[0020] The first preferred embodiment according to the invention consists in the stack comprising at least one silver-based functional layer modified according to the invention, which layer is contiguous with a standard layer at least based on AlN (or one which is also modified according to the invention): in this case, it is more a question of adapting the Ac layer to the AlN layer.

[0021] The second preferred embodiment according to the invention, as an alternative or in addition to the first embodiment, consists in the stack comprising at least one AlN-based layer modified according to the invention, which layer is contiguous with a standard silver-based functional layer (or one which is also modified according to the invention). The reverse approach is adopted here, in which it is more a question of seeking to make the AlN more “compatible” with the silver.

[0022] One possible variant of the invention consists in placing the functional layer (or at least one of them or each of them if the stack comprises more than one of them) so as to be in contact on one of its faces with an AlN layer (one of the two layers or both of them being modified according to the invention), the other face of the functional layer being in contact with a layer of a metal oxide or of a mixture of metal oxides, such as ZnO, TiO₂, SnO₂, Nb₂O₅, Ta₂O₅. As the aforementioned PCT patent application stresses, it is in fact advantageous, optionally, to provided, beneath the silver-based layers, layers made of an oxide of the ZnO type which provide very intimate contact with the silver.

[0023] This oxide layer may be the last of a superposition of oxide and/or nitride layers, such as AlN or Si₃N₄ layers.

[0024] Another variant (which can be added to the previous one) consists in placing the AlN layer modified according to the invention so as to be in direct contact with the silver layer and to have a greater concentration of metal M′ near its interface with this silver layer. In other words, it is possible to have a concentration gradient of metal M′ in the AlN layer, with a concentration increasing towards the AlN/Ag interface. The industrially simplest embodiment consists in fact in dividing the AlN layer into several “strata”, the closest stratum to the silver layer being the richest in metal M′ (obtained from an Al-M′ target) and the rest of the layer being depleted in metal M′ or even completely devoid of metal M′ (Al target). Thus, it is possible to have the following bilayer structure:

AlN:M′/AlN or AlN/M′:AlN.

[0025] This is because it can be slightly prejudicial in terms of light absorption to have AlN containing a metal whose nitride is relatively absorbent (as is the case with titanium for example) over a significant thickness. Thus, by “duplicating” the layer it is possible to increase the adhesion to silver without any risk of optically degrading the stack.

[0026] There are three non-limiting embodiments of the invention with two silver layers:

[0027]

the sequence: substrate/metal oxide/Ag⁽¹⁾)/metal oxide/Ag⁽²⁾/AlN

[0028]

the sequence: substrate/AlN/Ag⁽¹⁾/metal oxide/Ag⁽²⁾/AlN

[0029] ⊂ the sequence: substrate/AlN/Ag⁽¹⁾/AlN/Ag⁽⁻⁾/AlN.

[0030] In all three cases, when there is direct contact between AlN and Ag, one or both of them is modified according to the invention. The term “metal oxide” is understood to mean a layer of a metal oxide or several different oxides, or a nitride layer AlN or Si₃N₄ “flanked” by oxide layers (or thin layers of metal of the Ti or NiCr type).

[0031] In the simplest variant with a metal oxide layer, TiO₂ is especially preferred.

[0032] It remains within the scope of the invention for one of the Ag functional layers not to follow the teaching of the invention, unlike the other, and to be, for example, in contact with an AlN or Si₃N₄ layer via a thin layer intended to increase their mutual adhesion, for example a titanium layer.

[0033] It is also possible within the scope of the invention to substitute an AlN layer or at least one of them with an Si₃N₄ layer, which may be chemically modified like the AlN.

[0034] The subject of the invention is also any glazing which incorporates the multilayer-coated substrate described above. In particular, this is laminated glazing using a PET-type flexible substrate coated with the layers according to the invention and laminated by means of two thermoplastic adhesive sheets of the polyvinyl butyral (PVB) or ethylene/vinyl acetate (EVA) type with two glass-type rigid substrates.

[0035] The glazing of the invention, whether monolithic, laminated or mounted as insulating double glazing, may be used in buildings or for equipping vehicles, especially as laminated side windows or windscreens.

[0036] The invention will be described below with the aid of specific non-limiting examples.

[0037] All the layers are deposited in a known way, by sputtering, on a PET sheet having a thickness of approximately 50 micrometers (this sheet being biaxially oriented in a known manner).

EXAMPLE 1

[0038] (the thicknesses of the layers indicated are in nm for all the examples)

[0039] PET/TiO₂/Ag/TiO₂/Ag/Ti:AlN 30 nm 10 nm

[0040] the Ti:AlN containing 1.5% Ti by weight with respect to Al, as is also the case in Examples 2 and 3. It is possible to vary this content, preferably within a range from 0.5 to 2.5%.

EXAMPLE 2

[0041] PET/AlN/Ag/TiO₂/Ag/Ti:AlN 30 nm 10 nm 56 nm 10 nm 40 nm

EXAMPLE 3

[0042] PET/TiO₂/Ag/Ti/TiO₂/ZnO/Ag/Ti:AlN 30 nm 10 nm 1 nm 56 nm 10 nm 40 nm

[0043] In Examples 1 and 2, metal layers, especially Ti layers of very small thickness, may optionally be interposed between the TiO₂ layers and the Ag layers. This is more particularly preferred on top of the first silver layer, as a “blocker” layer to prevent any degradation of the silver during the deposition of the TiO₂ layer in an oxidizing reactive atmosphere. Thus, between 1 and 2 nm of Ti may be provided on top of the first Ag layer.

[0044] It is also possible to provide a very thin, but not necessarily continuous, metal layer directly under the second silver layer, for example a layer also made of titanium and with a thickness, for example, of between 0.2 and 1 nm. 

1. Flexible or rigid, transparent substrate provided with a stack of thin layers, which includes at least one functional layer predominantly based on silver Ag placed between two coatings of dielectric material, at least one of the coatings comprising a layer predominantly based on aluminium nitride AlN, characterized in that the functional layer or at least one of the functional layers is modified by incorporating at least one minor metal M other than Ag and/or the said AlN-based layer, or at least one of them, is modified by incorporating at least one metal M′ which is in a minor amount compared with the aluminium.
 2. Substrate according to claim 1, characterized in that the stack comprises n functional layers and n+1 coatings of dielectric material, with n≧2.
 3. Substrate according to one of the preceding claims, characterized in that the rigid substrate s made of glass or a polymer material of the polycarbonate PC or polymethyl methacrylate PMMA type.
 4. Substrate according to either of claims 1 and 2, characterized in that the substrate is flexible and based on a polymer, especially polyurethane PU or polyethylene terephthalate PET.
 5. Substrate according to one of the preceding claims, characterized in that the metal M is aluminium Al or copper Cu or gold Au.
 6. Substrate according to one of the preceding claims, characterized in that the modified functional layer comprises from 0 to 10%, especially from 0.5 to 2%, by weight of metal M.
 7. Substrate according to one of the preceding claims, characterized in that the metal M′ is chosen from Zn, Ti, Sn, Mn, Mg, Ag.
 8. Substrate according to one of the preceding claims, characterized in that the AlN-based layer comprises from 0.1 to 10% by freight, especially from 0.5 to 2% by weight, of M′ with respect to Al.
 9. Substrate according to one of the preceding claims, characterized in that the stack comprises at least one functional layer modified by incorporating metal M, this layer being contiguous with a modified or unmodified AlN-based layer.
 10. Substrate according to one of the preceding claims, characterized in that the stack comprises at least one AlN-based layer modified by incorporating metal M′, this layer being contiguous with a modified or unmodified silver-based functional layer.
 11. Substrate according to either of claims 9 and 10, characterized in that the said functional layer is provided, on its face on the opposite side from that which is in contact with the AlN-based layer, with a layer based on a metal oxide, especially one chosen from ZnO, TiO₂, SnO₂, Nb₂O₅, Ta₂O₅.
 12. Substrate according to one of the preceding claims, characterized in that the AlN-based layer modified by incorporating a metal M′ is in direct contact with a silver-based functional layer and in that it has a greater concentration of metal A′ near its interface with the said functional layer.
 13. Substrate according to claim 12, characterized in that the AlN-based layer is divided into several strata, including a stratum richest in metal M′ on the same side as the functional layer with which it is in contact, the rest of the AlN-based layer being depleted in metal M′ or completely devoid of metal M′, especially being in the form of an M′:AlN/AlN bilayer.
 14. Substrate according to one of the preceding claims, characterized in that the stack of layers is of the type: substrate/metal oxide/Ag⁽¹⁾/metal oxide/Ag⁽²⁾/AlN with the AgC⁽²⁾ second layer modified by incorporating the metal M and/or the AlN layer modified by incorporating the metal M′.
 15. Substrate according to one of the preceding claims, characterized in that the stack of layers is of the type: substrate/AlN/Ag/AlN/Ag/AlN with at least one of the two Ag layers modified by incorporating the metal M and/or at least one of the two AlN layers modified by incorporating the metal M′.
 16. Substrate according to one of claims 1 to 13, characterized in that the stack of layers is of the type: substrate/AlN/Ag/metal oxide/Ag/AlN with at least one of the two Ag layers modified by incorporating the metal M and/or at least one of the three AlN layers modified by incorporating the metal M′.
 17. Laminated glazing according to one of the preceding claims, characterized in that it incorporates a polymer-based flexible substrate coated according to one of the preceding claims. 